WO2020066367A1 - Feuille réfléchissante - Google Patents

Feuille réfléchissante Download PDF

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Publication number
WO2020066367A1
WO2020066367A1 PCT/JP2019/032419 JP2019032419W WO2020066367A1 WO 2020066367 A1 WO2020066367 A1 WO 2020066367A1 JP 2019032419 W JP2019032419 W JP 2019032419W WO 2020066367 A1 WO2020066367 A1 WO 2020066367A1
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Prior art keywords
layer
liquid crystal
reflection
reflective
cholesteric liquid
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PCT/JP2019/032419
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English (en)
Japanese (ja)
Inventor
誠 石黒
秀樹 兼岩
信彦 一原
昌 山本
竜二 実藤
永井　道夫
Original Assignee
富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020548154A priority Critical patent/JP7175994B2/ja
Publication of WO2020066367A1 publication Critical patent/WO2020066367A1/fr
Priority to US17/214,076 priority patent/US11789185B2/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0284—Diffusing elements; Afocal elements characterized by the use used in reflection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0263—Diffusing elements; Afocal elements characterised by the diffusing properties with positional variation of the diffusing properties, e.g. gradient or patterned diffuser
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks

Definitions

  • the present invention relates to a reflection sheet used for a decorative sheet or the like.
  • a cholesteric liquid crystal layer having a fixed cholesteric liquid crystal phase is known as a layer having a property of selectively reflecting either right-handed circularly polarized light or left-handed circularly polarized light in a specific wavelength band. Therefore, it has been developed for various uses, and for example, its use as a decorative sheet is being studied.
  • Patent Literature 1 describes a decorative sheet formed by laminating two cholesteric liquid crystal layers having different rotating directions of reflected circularly polarized light.
  • Patent Document 1 describes that in a two-layer cholesteric liquid crystal layer, a better metallic luster can be obtained by changing the helical pitch continuously or stepwise in the thickness direction. .
  • the decorative sheet has a diffuse reflection property.
  • the reflection of light by the cholesteric liquid crystal layer is so-called specular reflection. For example, light incident from the normal direction is reflected in the normal direction.
  • Patent Document 2 describes that in forming a cholesteric liquid crystal layer, the direction of the alignment regulating force of the alignment film is made random, and the direction of the director of the liquid crystal compound in contact with the alignment film is made random. Have been.
  • the cross section of the cholesteric liquid crystal layer is observed with a scanning electron microscope, a stripe pattern of a bright portion and a dark portion is observed due to the cholesteric liquid crystal phase.
  • the stripes of the bright and dark portions are linear in the plane direction.
  • the helical axis of the liquid crystal compound is oriented in various directions.
  • a cholesteric liquid crystal layer has a wavy structure in which bright and dark stripes are wavy in the thickness direction.
  • the cholesteric liquid crystal layer having such a wavy structure does not specularly reflect incident light but diffusely reflects light in accordance with the direction of the helical axis.
  • a reflection sheet using a cholesteric liquid crystal layer used for a decorative sheet or the like it is preferable that light in a wide wavelength band can be reflected with good diffusivity.
  • a reflection sheet that can reflect light in a wide wavelength band with good diffusivity and has good characteristics with no noticeable unevenness using a cholesteric liquid crystal layer has not yet been realized.
  • An object of the present invention is to solve such problems of the related art, and in a reflection sheet using a cholesteric liquid crystal layer, light in a wide wavelength band can be reflected with good diffusivity, and unevenness is not noticeable. Another object of the present invention is to provide a reflection sheet having excellent characteristics.
  • the present invention has the following configuration. [1] It has a configuration in which a plurality of reflective layers each having a fixed cholesteric liquid crystal phase are laminated, The reflective layer, in a cross section observed by a scanning electron microscope, at least a part of the bright part and the dark part derived from the cholesteric liquid crystal phase have a wavy structure, At least one of the reflective layers has a pitch gradient structure in which the helical pitch changes in the thickness direction, When a reflective layer having a surface other than the surface of the reflective layer is formed as a lower reflective layer, the lower reflective layer is thinner than the other reflective layers. Reflective sheet.
  • the reflection sheet according to any one of [1] to [9] including a support and an underlayer provided on one surface of the support, wherein the lower reflective layer is adjacent to the underlayer.
  • a reflective sheet using a cholesteric liquid crystal layer which is capable of reflecting light in a wide wavelength band with good diffusivity, and has excellent characteristics with less noticeable unevenness.
  • FIG. 1 is a sectional view conceptually showing an example of the reflection sheet of the present invention.
  • FIG. 2 is a conceptual diagram for explaining light reflection by the cholesteric liquid crystal layer.
  • FIG. 3 is a conceptual diagram for explaining light reflection by the cholesteric liquid crystal layer.
  • FIG. 4 is a conceptual diagram for explaining the peak-to-peak distance of the wavy structure.
  • the numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
  • the liquid crystal composition and the liquid crystal compound also include those which no longer exhibit liquid crystallinity due to curing or the like.
  • the integrated reflectivity IR ( ⁇ ) at the wavelength ⁇ of the reflection sheet is set so that light is incident from the reflection layer surface (cholesteric liquid crystal layer surface) of the reflection sheet by a spectrophotometer (manufactured by JASCO Corporation; 550) to which a large integrating sphere device (ILV-471, manufactured by JASCO Corporation) is attached, and the measurement may be performed by an optical trap.
  • a spectrophotometer manufactured by JASCO Corporation; 550
  • IMV-471 large integrating sphere device
  • the specular reflectance SR ( ⁇ ) at the wavelength ⁇ of the reflection sheet is absolutely reflected by a spectrophotometer (V-550, manufactured by JASCO Corporation) so that light is incident from the reflection layer surface of the reflection sheet.
  • the measurement may be performed at an incident angle of 5 ° using a device equipped with a rate measuring device (ARV-474, manufactured by JASCO Corporation).
  • the cure rate is a value obtained by measuring the consumption rate of a polymerizable functional group using an IR (Infrared) absorption spectrum.
  • IR Infrared
  • the sample is cut obliquely to expose the film thickness direction in the plane.
  • An IR absorption spectrum of the generated sample section is measured by an ATR-IR (Attenuated Total Reflection-infrared spectroscopy) method. From the ratio of the absorption intensity based on the carbonyl group around 1720 cm -1 and the absorption intensity around 810 cm -1 based on the carbon-carbon double bond in the obtained absorption spectrum, the consumption rate of the polymerizable functional group can be quantified. .
  • the generated sample section is divided into five equal parts in the film thickness direction, and the outermost two areas correspond to the IR by the ATR-IR method described above. What is necessary is just to obtain by measuring an absorption spectrum.
  • the selective reflection center wavelength of the reflection layer (cholesteric liquid crystal layer) and the half-value width in a selective reflection wavelength band may be obtained by the following method. That is, when the integrated reflectance is measured by the above-described method, a peak-shaped (upwardly convex) integrated reflectance spectrum waveform having the wavelength on the horizontal axis is obtained. At this time, the average reflectance (arithmetic average) of the maximum value and the minimum value of the integrated reflectance is obtained, and of the two wavelengths at the two intersections of the waveform and the average reflectance, the value of the wavelength on the short wave side is ⁇ (nm).
  • the value of the wavelength on the long wave side is ⁇ (nm), and is calculated by the following equation.
  • Selective reflection center wavelength ( ⁇ + ⁇ ) / 2
  • Half width ( ⁇ - ⁇ )
  • the waveform of the integrated reflectance spectrum of the integrated reflectance may be distorted in a sawtooth shape.
  • the average reflectance (arithmetic average) of the maximum value and the minimum value of the specular reflectance is obtained from the spectrum waveform of the specular reflectance described above, and two wavelengths at two intersections of the waveform and the average reflectance are obtained.
  • the selective reflection wavelength may be calculated by the above equation, where the wavelength value on the short wave side is ⁇ (nm) and the wavelength value on the long wave side is ⁇ (nm).
  • a method of measuring a selective reflection center wavelength and a half width by measuring a transmission spectrum of a sample with Axoscan of Axometrix or the like. When the transmission spectrum is measured, a valley-shaped (convex downward) transmission spectrum waveform having the wavelength on the horizontal axis is obtained.
  • the average reflectance (arithmetic average) of the maximum value and the minimum value of the transmittance is obtained, and of the two wavelengths at the two intersections of the waveform and the average transmittance, the value of the wavelength on the short wave side is ⁇ (nm),
  • the selective reflection center wavelength and the half-value width are calculated by the above-described equations.
  • FIG. 1 conceptually shows an example of the reflection sheet of the present invention.
  • the reflective sheet 10 shown in FIG. 1 includes a support 12, an underlayer 14 formed on one surface of the support 12, a first reflective layer 16 formed on the surface of the underlayer 14, and a first reflective layer 16. And a second reflective layer 18 formed on the surface of the second reflective layer 18. Therefore, the first reflective layer 16 formed on the surface of the base layer 14 and not the reflective layer becomes the lower reflective layer in the present invention.
  • the upper part in the drawing, that is, the second reflective layer 18 side is also referred to as upper
  • the lower part in the drawing, that is, the support 12 side is also referred to as lower.
  • FIG. 1 is a view conceptually showing a state in which a cross section of the reflection sheet 10 is observed with a scanning electron microscope (SEM) (the same applies to FIGS. 2 and 3 described later).
  • SEM scanning electron microscope
  • Each of the first reflection layer 16 and the second reflection layer 18 is a cholesteric liquid crystal layer in which a cholesteric liquid crystal phase is fixed. Therefore, in the first reflection layer 16 and the second reflection layer 18, a stripe pattern of a bright portion B and a dark portion D derived from the cholesteric liquid crystal phase is observed.
  • the support 12 supports the base layer 14, the first reflection layer 16 and the second reflection layer 18.
  • the support 12 is not limited, and a known sheet (film, plate) can be used.
  • a resin film made of polyester such as polyethylene terephthalate (PET), polycarbonate (PC), acrylic resin, epoxy resin, polyurethane, cycloolefin resin, polyamide, polyolefin, cellulose derivative, silicone and the like are exemplified.
  • the support 12 may be a peelable support 12 that can be peeled from the underlayer 14.
  • the support 12 may be a releasable support 12 that can be separated from the first reflection layer 16.
  • the releasable support 12 include a resin film made of a cellulose derivative, a cycloolefin resin, a resin containing polyethylene terephthalate, or the like. Among them, a resin film made of a resin containing polyethylene terephthalate is preferably exemplified.
  • a known release layer may be provided between the non-peelable support 12 and the underlayer 14 to form the peelable support 12.
  • the surface of the non-peelable support 12 may be subjected to a known surface treatment to form the releasable support 12.
  • the peelable support 12 is, for example, attached to another reflective sheet such as a decorative sheet and various optical devices and the like, and then attached to a component of the image display device to manufacture the image display device. After being adhered to the interior member for a car, the sheet is peeled off from the reflection sheet (the base layer 14).
  • the thickness of the support 12 is preferably 20 ⁇ m or more, and more preferably 40 ⁇ m or more. Further, the thickness of the peelable support 12 is preferably 35 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 80 ⁇ m or more. When the thickness of the support 12 serving as a base material when forming the reflective layers such as the base layer 14 and the first reflective layer 16 is set to 20 ⁇ m or more, particularly, the thickness of the peelable support 12 is set to 50 ⁇ m or more. A layer without unevenness can be obtained.
  • the upper limit of the thickness of the support 12 is not limited, but is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and still more preferably 300 ⁇ m or less, from the viewpoint that the reflection sheet 10 can be prevented from becoming unnecessarily thick.
  • an underlayer 14 is formed on a support 12.
  • the underlayer 14 serves as a protective layer for preventing the support 12 from being damaged by a solvent when forming a first reflective layer 16 to be described later, and a surface on which the first reflective layer 16 is formed.
  • a layer that reduces the difference in surface energy between the first reflective layer 16 and a material for forming the first reflective layer 16 (a liquid crystal composition described later) is exemplified.
  • the base layer 14 is used to protect the first reflective layer 16 after the support 12 is peeled off by attaching the reflective sheet 10 to another member. It may act as a layer.
  • the material for forming the underlayer 14 is not limited, and various known materials can be used according to the function required for the underlayer 14.
  • Examples of a material for forming the underlayer 14 include a polyacrylate resin, a polymethacrylate resin, a polyester resin, a polyolefin resin, an epoxy resin, a polyamide resin, and a polyimide resin. Among them, a polyacrylate resin and a polymethacrylate resin are preferably exemplified.
  • an underlayer formed by applying and curing a non-liquid crystalline composition containing a (meth) acrylate monomer is exemplified.
  • the thickness of the underlayer 14 is not limited, and a thickness that can satisfy required characteristics may be appropriately set according to the material of the underlayer 14.
  • the thickness of the underlayer 14 is preferably 0.01 to 8 ⁇ m, more preferably 0.05 to 3 ⁇ m.
  • the thickness of the underlayer 14 is preferably 0.01 to 8 ⁇ m and 2.5 to 2.5 ⁇ m in order to prevent the extraction of components from the support 12 from affecting the reflective layer. ⁇ 6 ⁇ m is more preferred.
  • the support 12 and the base layer 14 are provided as preferred embodiments. Therefore, the reflective sheet of the present invention may not have one or both of the support 12 and the underlayer 14.
  • a first reflection layer 16 (lower reflection layer) is formed on the surface of the base layer 14, and a second reflection layer 18 is formed on the surface of the first reflection layer 16.
  • the first reflective layer 16 and the second reflective layer 18 are both collective liquid crystal layers in which the cholesteric liquid crystal phase is fixed.
  • the first reflective layer 16 is formed on the base layer 14 other than the second reflective layer 18 which is a reflective layer. Therefore, the first reflective layer 16 is the lower reflective layer in the present invention.
  • Cholesteric liquid crystal phases are known to exhibit selective reflectivity at specific wavelengths.
  • the longer the helical pitch the longer the selective reflection center wavelength of the cholesteric liquid crystal phase becomes.
  • the helical pitch is one pitch of the helical structure of the cholesteric liquid crystal phase (helical period).
  • the spiral that is, the die of the liquid crystal compound constituting the cholesteric liquid crystal phase.
  • This is the length of the helical axis in which the rotator rotates 360 °.
  • the director is, for example, in the long axis direction in the case of a rod-shaped liquid crystal.
  • the helical pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used together with the liquid crystal compound when forming the cholesteric liquid crystal layer, and the concentration of the chiral agent added. Therefore, a desired helical pitch can be obtained by adjusting these.
  • the pitch adjustment is described in Fujifilm Research Report No. 50 (2005) p. 60-63 has a detailed description.
  • For the method of measuring the sense and pitch of the helix use the method described in "Introduction to Liquid Crystal Chemistry Experiments", edited by The Liquid Crystal Society of Japan, Sigma Publishing, 2007, p. 46, and "Liquid Crystal Handbook", Liquid Crystal Handbook Editing Committee, Maruzen, p. 196 be able to.
  • the cholesteric liquid crystal phase exhibits selective reflectivity with respect to left or right circularly polarized light at a specific wavelength. Whether the reflected light is right circularly polarized light or left circularly polarized light depends on the twist direction (sense) of the helix of the cholesteric liquid crystal phase.
  • the selective reflection of circularly polarized light by the cholesteric liquid crystal phase reflects right circularly polarized light when the helical twist direction of the cholesteric liquid crystal layer is right, and reflects left circularly polarized light when the helical twist direction is left.
  • the direction of rotation of the cholesteric liquid crystal phase can be adjusted by the type of the liquid crystal compound forming the cholesteric liquid crystal layer and / or the type of the added chiral agent.
  • both the first reflection layer 16 and the second reflection layer 18, which are cholesteric liquid crystal layers have a pitch gradient structure in which the helical pitch changes in the thickness direction.
  • the thickness direction is the vertical direction in FIG.
  • the helical pitch of the first reflection layer 16 and the second reflection layer 18 gradually increases upward. That is, in the first reflection layer 16 and the second reflection layer 18, the selective reflection center wavelength, that is, the wavelength band of the light to be selectively reflected gradually becomes longer wavelength upward.
  • a pitch gradient structure in which the helical pitch changes in the thickness direction in the cholesteric liquid crystal layer is also referred to as a PG structure (Pitch Gradient structure).
  • a cholesteric liquid crystal layer having a PG structure uses a chiral agent that undergoes return isomerization, dimerization, and isomerization and dimerization by light irradiation to change the helical inducing power (HTP: Helical Twisting Power).
  • HTP Helical Twisting Power
  • the liquid crystal composition can be formed by irradiating light having a wavelength that changes the HTP of the chiral agent. For example, by using a chiral agent whose HTP is reduced by light irradiation, the HTP of the chiral agent is reduced by light irradiation.
  • the irradiated light is absorbed by the material for forming the cholesteric liquid crystal layer. Therefore, for example, when light is irradiated from above, the light irradiation amount gradually decreases from above to below. That is, the amount of decrease in the HTP of the chiral agent gradually decreases from above to below. Therefore, in the upper part where the HTP is greatly reduced, the helical pitch is longer because the induction of the helix is small, and in the lower part where the decrease in the HTP is small, the helical pitch is shorter because the chiral agent originally induces the helix with the HTP that the chiral agent has. Become.
  • the cholesteric liquid crystal layer selectively reflects long-wavelength light upward, and selectively reflects short-wavelength light below in comparison with the upper direction. Therefore, by using a cholesteric liquid crystal layer having a PG structure in which the helical pitch changes in the thickness direction, light in a wide wavelength band can be selectively reflected.
  • the first reflection layer 16 and the second reflection layer 18, which are cholesteric liquid crystal layers, have a bright portion B in the thickness direction (vertical direction in FIG. 1) due to the cholesteric liquid crystal phase in the cross section observed by SEM.
  • a stripe pattern in which (light lines) and dark portions D (dark lines) are alternately laminated is observed.
  • the first reflection layer 16 and the second reflection layer 18 are layers having a cholesteric liquid crystal structure and a structure in which the angle between the helical axis and the surface of the reflection layer changes periodically.
  • both the reflective layers have a cholesteric liquid crystal structure
  • the cholesteric liquid crystal structure gives a stripe pattern of a bright portion B and a dark portion D in a cross-sectional view of the reflective layer observed by SEM.
  • This is a reflective layer in which the angle between the line and the surface of the reflective layer changes periodically.
  • the wavy structure means that at least one region M in which a cholesteric liquid crystal layer (reflection layer) has an absolute angle of 5 ° or more with respect to a plane of a continuous line of a light portion B or a dark portion D forming a stripe pattern.
  • a peak or a valley having an inclination angle of 0 ° which exists and is located closest to the area M in the plane direction.
  • the peak or the valley having an inclination angle of 0 ° includes a convex shape and a concave shape, but the inclination angle of 0 ° also includes a step-like and a shelf-like point.
  • FIG. 2 conceptually shows a cross section of a layer formed by fixing a general cholesteric liquid crystal phase.
  • a stripe pattern of a bright portion B and a dark portion D is observed. That is, in the cross section of the cholesteric liquid crystal layer, a layered structure in which light portions B and dark portions D are alternately stacked in the thickness direction is observed.
  • two repetitions of the bright portion B and the dark portion D correspond to a helical pitch. From this, the helical pitch of the cholesteric liquid crystal layer, that is, the reflection layer, can be measured from the SEM sectional view. Two repetitions of the bright part B and the dark part D are three bright parts and two dark parts.
  • the stripe pattern (layered structure) of the light portion B and the dark portion D is formed so as to be parallel to the surface of the substrate 30, as shown in FIG.
  • Such a cholesteric liquid crystal layer 32 exhibits specular reflectivity. That is, when light is incident from the normal direction of the cholesteric liquid crystal layer 32, the light is reflected in the normal direction, but the light is hardly reflected in the oblique direction, and is inferior in diffuse reflectivity (arrow in FIG. 2). reference).
  • the bright part B and the dark part D have a wavy structure (undulation structure), as in the cholesteric liquid crystal layer 34 whose cross section is conceptually shown in FIG. 3, the normal direction of the cholesteric liquid crystal layer 34 is used. As shown in FIG. 3, a part of the incident light is reflected in an oblique direction because there is a region where the helical axis of the liquid crystal compound is inclined as conceptually shown in FIG. reference). That is, in the cholesteric liquid crystal layer in which the cholesteric liquid crystal phase is fixed, since the bright portion B and the dark portion D have a wavy structure, a reflective layer having high diffuse reflection can be realized.
  • both the first reflection layer 16 and the second reflection layer 18 have a wavy structure in a cross section observed by an SEM in a bright portion B and a dark portion D derived from a cholesteric liquid crystal phase.
  • the configuration in which the bright portion B and the dark portion D derived from the cholesteric liquid crystal phase have a wavy structure in the cross section of the cholesteric liquid crystal layer (reflection layer) observed by SEM will be referred to simply as “cholesteric liquid crystal layer (reflection layer)”.
  • Layer has a wavy structure ”.
  • a cholesteric liquid crystal layer having a wavy structure can be formed by forming a cholesteric liquid crystal layer on a surface on which alignment processing such as rubbing is not performed. Therefore, in the illustrated example, the first reflective layer 16 having a wavy structure can be formed by forming the first reflective layer 16 without subjecting the base layer 14 to an alignment process such as a rubbing process. That is, when the first reflective layer 16 which is a cholesteric liquid crystal layer is formed on the underlayer 14 on which no alignment treatment is performed, there is no horizontal alignment regulating force for the liquid crystal compound. On the surface, the liquid crystal compound is oriented in various directions.
  • the helical axes of the liquid crystal compound constituting the cholesteric liquid crystal phase are oriented in various directions.
  • the stripes of the light portion B and the dark portion D are formed.
  • the pattern has a wavy structure.
  • the upper cholesteric liquid crystal layer follows the orientation of the surface of the lower cholesteric liquid crystal layer.
  • the alignment state of the upper cholesteric liquid crystal layer follows the alignment state of the surface of the lower cholesteric liquid crystal layer. Therefore, when the second reflection layer 18 which is a cholesteric liquid crystal layer is formed on the first reflection layer 16 having a wavy structure, the second reflection layer 18 follows the alignment state of the surface of the first reflection layer 16.
  • the second reflection layer 18 is also a cholesteric liquid crystal layer having the same wavy structure as the first reflection layer 16. Therefore, in the reflection sheet 10, the first reflection layer 16 and the second reflection layer 18 have the same wavy structure in which the period of the wave, that is, the unevenness of the wavy structure is almost the same.
  • the amplitude of the wave may be the same or different between the first reflection layer 16 and the second reflection layer 18.
  • HTP of a general chiral agent is reduced by light irradiation.
  • Light for changing the HTP of the chiral agent is usually irradiated from the side opposite to the support 12.
  • the second reflective layer 18 and the reflective layer formed after the second reflective layer 18 are light for changing the HTP of the chiral agent in order to eliminate the influence of the previously formed reflective layer (cholesteric liquid crystal layer). Is preferably irradiated from the side opposite to the support 12.
  • the amplitudes of the waves may be the same or different, and the regions having the same and different waves may be mixed.
  • the bright portion B and the dark portion D of the first reflection layer 16 and the second reflection layer 18 are not limited to having a wavy structure throughout, and at least a part thereof has a wavy structure. What is necessary is just a structure. That is, in the reflection sheet 10 of the present invention, the bright portion B and the dark portion D in the first reflection layer 16 and the second reflection layer 18 may include a region that does not have a wavy structure due to a defect portion or the like generated here. Good.
  • the reflection sheet of the present invention has a plurality of reflection layers (cholesteric liquid crystal layers) having a wavy structure, and at least one of the reflection layers has a PG structure in which a helical pitch changes in a thickness direction. Further, the lower reflective layer having a surface other than the reflective layer is thinner than other reflective layers having the reflective layer.
  • the illustrated reflection sheet 10 has two reflection layers, a first reflection layer 16 and a second reflection layer 18. In a preferred embodiment, both reflection layers have a PG structure, and the first reflection layer, which is a lower reflection layer, is provided. Layer 16 is thinner than second reflective layer 18. In the illustrated example, the second reflective layer 18 is the outermost layer.
  • the reflection sheet 10 of the present invention having such a configuration can reflect light in a wide wavelength band with good diffusivity, and furthermore has uneven color and light quantity caused by a defect in the reflection layer (cholesteric liquid crystal layer). Thus, a reflection sheet having excellent characteristics, which is not noticeable, is realized.
  • the cholesteric liquid crystal layer has a bright portion B and a bright portion B derived from the cholesteric liquid crystal phase in the cross section observed by the SEM. It is preferable that the dark portion D has a wavy structure. Further, in a reflection sheet using a cholesteric liquid crystal layer as a reflection layer, in order to widen a selective reflection wavelength band, it is preferable to have a PG structure in which a helical pitch changes in a thickness direction of the cholesteric liquid crystal layer.
  • the PG structure uses a chiral agent whose HTP changes by light irradiation, and irradiates light having a wavelength that the chiral agent absorbs at the time of forming a cholesteric liquid crystal layer, so that the PG structure has a thickness direction. It can be obtained by changing the amount of light irradiation, that is, the amount of change in HTP. Therefore, the greater the difference in the light irradiation amount in forming the cholesteric liquid crystal layer in the thickness direction, the wider the selective reflection wavelength band can be.
  • a cholesteric liquid crystal layer having a wavy structure can be obtained by forming a cholesteric liquid crystal layer on a surface on which alignment processing is not performed. That is, the cholesteric liquid crystal layer having a wavy structure is formed in a state where there is no horizontal alignment regulating force for the liquid crystal compound. Therefore, a defective portion such as a broken portion, a branched portion, an extremely bent portion, and a folded portion may be formed on at least one of the light portion B and the dark portion D of the cholesteric liquid crystal layer.
  • the PG structure is a structure in which the helical pitch of the cholesteric liquid crystal phase changes.
  • the cholesteric liquid crystal layer having the PG structure acts to amplify the cholesteric liquid crystal layer, if there is a defect, in accordance with the change in the helical pitch, and the defect is conspicuous.
  • the effect of amplifying this defect increases as the cholesteric liquid crystal layer becomes thicker.
  • a reflective sheet having a wavy structure and a PG structure and using a cholesteric liquid crystal layer having a certain thickness as a reflective layer has a more conspicuous defect in the reflective layer than a normal cholesteric liquid crystal layer. Then, color unevenness and reflected light amount unevenness like an annual ring are generated.
  • the reflection sheet 10 of the present invention has the first reflection layer 16 and the second reflection layer 18 having the corrugated structure and the PG structure, and the thickness of the first reflection layer 16 is the second reflection layer 18. Thinner than the thickness of.
  • the first reflective layer 16 is formed on the underlayer 14 having no alignment regulating force, defects easily occur.
  • the first reflection layer 16 is oriented in a wavy structure, and has a certain degree of orientation control force on the surface.
  • the second reflection layer 18 follows the orientation state of the surface of the first reflection layer 16.
  • the second reflective layer 18 formed thereon is subjected to an alignment treatment. This is the same as when formed on the formed surface. Therefore, although the second reflective layer 18 has a wavy structure, the generation of defects can be greatly suppressed, and thus the defects are not noticeable even when the second reflective layer 18 is thick. In addition, since the first reflective layer 16 having many defects is thinner than the second reflective layer 18, even if it has a PG structure, the effect of amplifying the defects is small and the defects can be made inconspicuous.
  • the second reflection layer 18 in the reflection sheet using the cholesteric liquid crystal layer having the wavy structure and the PG structure also as the reflection layer, the second reflection layer 18 can be thickened, and the selective reflection wavelength band is wide and good. It is possible to realize a reflection sheet having excellent diffuse reflection properties and excellent characteristics with no noticeable defects.
  • both the first reflection layer 16 and the second reflection layer 18 have a PG structure, but the present invention is not limited to this. That is, in the reflection sheet of the present invention, the first reflection layer 16 may have a PG structure, the second reflection layer 18 may have a structure having a uniform helical pitch, and the first reflection layer 16 may have a helical pitch.
  • the second reflective layer 18 may have a uniform structure, and may have a PG structure. However, in the reflection sheet of the present invention, it is preferable that at least the second reflection layer 18 has a PG structure, and as shown in the illustrated example, both the first reflection layer 16 and the second reflection layer 18 have a PG structure. Is more preferred.
  • the thickness of the first reflection layer 16 is not limited, and may be thinner than the second reflection layer 18 (other reflection layers).
  • the thickness of the first reflective layer 16 is preferably 3.5 ⁇ m or less, more preferably 3.2 ⁇ m or less, and even more preferably 2.7 ⁇ m or less.
  • the thickness of the first reflective layer 16 is preferably 0.3 ⁇ m or more from the viewpoint that a sufficient alignment regulating force can be exerted on the second reflective layer 18.
  • the thickness of the second reflection layer 18 (a reflection layer other than the first reflection layer 16) is not limited, and may be any thickness as long as it is thicker than the first reflection layer 16.
  • the thickness of the second reflective layer 18 is preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, and still more preferably 6 ⁇ m or more. Setting the thickness of the second reflective layer 18 to 4 ⁇ m or more is preferable in that light in a wider wavelength band can be selectively reflected and a higher reflectance can be obtained.
  • the thickness of the second reflective layer 18 is preferably 7 ⁇ m or less from the viewpoint that the reflection sheet 10 can be prevented from being unnecessarily thick.
  • the thickness difference between the first reflective layer 16 and the second reflective layer 18 is not limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and still more preferably 2.5 ⁇ m or more.
  • the distance between the peaks of the wavy structure and the amplitude (wave height) are not limited.
  • the wavy structure of the first reflective layer 16 preferably has an average value of the peak-to-peak distance of 0.5 to 50 ⁇ m from the viewpoint that a wavy structure with few defects can be formed and more excellent diffuse reflectivity can be obtained. It is more preferably from 0.5 to 20 ⁇ m, even more preferably from 2.5 to 10 ⁇ m.
  • the second reflective layer 18 follows the wavy structure of the first reflective layer 16, the average value of the peak-to-peak distance of the second reflective layer 18 is substantially the same as that of the first reflective layer 16. .
  • the peak-to-peak distance of the wavy structure is, as conceptually shown in FIG. 4, the distance p between the closest convex vertices in the wavy structure.
  • the average value of the distance between peaks is specifically measured as follows. First, the cholesteric liquid crystal is determined for the two peaks (or valleys) having an inclination angle of 0 ° which are closest to the above-described region M with the absolute value of the inclination angle with respect to the plane of the cholesteric liquid crystal layer being 5 ° or more. Measure the distance of the layer in the plane direction. Such measurement is performed for the length of the cholesteric liquid crystal layer in the cross-section major axis direction of 100 ⁇ m, and the value obtained by arithmetically averaging the entire film thickness is defined as the average value of the distance between peaks.
  • the wavelength band in which the first reflection layer 16 selectively reflects and the wavelength band in which the second reflection layer 18 selectively reflects there is no limitation on the wavelength band in which the first reflection layer 16 selectively reflects and the wavelength band in which the second reflection layer 18 selectively reflects.
  • the setting may be appropriately made accordingly. Therefore, the wavelength band where the first reflection layer 16 selectively reflects and the wavelength band where the second reflection layer 18 selectively reflects may be the same or different.
  • the first reflection layer 16 and the second reflection layer 18 have different reflection wavelength bands, they may have overlapping wavelength bands or may not have overlapping wavelength bands.
  • the circularly polarized light reflected by the first reflective layer 16 and the circularly polarized light reflected by the second reflective layer 18 may have the same or different turning directions. Regarding the above points, the same applies to each reflective layer when three or more reflective layers are provided.
  • the reflective sheet of the present invention may have three or more reflective layers.
  • the turning direction of the circularly polarized light reflected by each reflective layer may be the same or different.
  • the reflective layer preferably has two layers.
  • a reflective sheet having two reflective layers having different rotation directions of circularly polarized light reflected from each other is exemplified.
  • the absorbance of the first reflection layer 16 and the second reflection layer 18 there is also no limitation on the absorbance of the first reflection layer 16 and the second reflection layer 18.
  • at least one of the first reflective layer 16 and the second reflective layer 18 has an absorbance of at least 3.2 for light having a wavelength of a maximum absorption wavelength ⁇ 10 nm absorbed by the contained chiral agent.
  • at least one of the first reflection layer 16 and the second reflection layer 18 has an absorbance of light having a wavelength of 313 nm of 3.2 or more.
  • the light absorption at a wavelength of the maximum absorption wavelength ⁇ 10 nm absorbed by the contained chiral agent is 3.2 or more, so that the reflection layer has isomerized light. Is more preferable because the amount of light is attenuated as the amount of the dye penetrates and the distribution of the amount of isomerized light reaching the film thickness direction can be formed.
  • the helical pitch of each of the PG structures of the first reflection layer 16 and the second reflection layer 18 is gradually increased in the upward direction.
  • the helical pitch of each of the PG structures of the first reflection layer 16 and the second reflection layer 18 may gradually increase downward. That is, in the reflection sheet of the present invention, the helical pitch of the PG structure may gradually increase toward the surface on which the first reflection layer 16 (lower reflection layer) is formed.
  • the helical pitch of the PG structure of the first reflective layer 16 gradually increases upward, and the PG structure of the second reflective layer 18 gradually increases the spiral pitch downward.
  • the direction in which the helical pitch gradually increases in the first reflection layer 16 and the second reflection layer 18 may be different. Regarding the above points, the same applies to each reflective layer when three or more reflective layers are provided.
  • the reflection sheet 10 of the present invention when forming the reflection layer (cholesteric liquid crystal layer), light irradiation for changing the HTP of the chiral agent is performed, and then light irradiation for curing the reflection layer is performed.
  • light irradiation for changing the HTP of the chiral agent and light irradiation for curing the reflective layer may be performed simultaneously. Since the chiral agent often reduces the HTP by light irradiation, the helical pitch in the thickness direction of each reflective layer in the reflective sheet of the present invention is longer for a higher curing rate and lower for a lower curing rate. Is preferred.
  • the integrated reflectance IR ( ⁇ ) at the wavelength ⁇ and the specular reflectance SR ( ⁇ ) at the wavelength ⁇ there is no limitation on the integrated reflectance IR ( ⁇ ) at the wavelength ⁇ and the specular reflectance SR ( ⁇ ) at the wavelength ⁇ .
  • the integrated reflectance IR ( ⁇ ) at the wavelength ⁇ is preferably at least twice the mirror reflectance SR ( ⁇ ) at the wavelength ⁇ , more preferably at least 2.5 times. Is more preferable, and more preferably three times or more.
  • the half-value width of the reflection spectrum in the wavelength band where the light is selectively reflected there is no limitation on the half-value width of the reflection spectrum in the wavelength band where the light is selectively reflected.
  • the half width in the integrated reflection spectrum is preferably 100 nm or more, more preferably 125 nm or more, and still more preferably 150 nm or more, from the viewpoint that light in a wider wavelength band can be reflected.
  • the first reflection layer 16 and the second reflection layer 18, that is, the cholesteric liquid crystal layer can be formed using a liquid crystal composition containing a liquid crystal compound and a chiral agent.
  • the liquid crystal compound used for forming the cholesteric liquid crystal layer preferably has two or more polymerizable groups. That is, a polymerizable liquid crystal compound is preferable. Further, the average molar extinction coefficient at 300 to 400 nm is preferably less than 5000.
  • the liquid crystal compound may be a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound, but is preferably a rod-shaped liquid crystal compound.
  • a rod-shaped liquid crystal compound forming the cholesteric liquid crystal structure a rod-shaped nematic liquid crystal compound is exemplified.
  • rod-shaped nematic liquid crystal compound examples include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines.
  • Phenyldioxane, tolan, alkenylcyclohexylbenzonitrile, and the like are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
  • Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group.
  • the polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods.
  • the number of polymerizable groups contained in the liquid crystal compound is preferably from 1 to 6 in one molecule, more preferably from 1 to 3.
  • the amount of the liquid crystal compound in the liquid crystal composition is not limited, but is preferably from 80 to 99.9% by mass, and more preferably from 85 to 99% by mass based on the solid content of the liquid crystal composition (the mass excluding the solvent). It is more preferably 0.5% by mass, and further preferably 90 to 99% by mass.
  • chiral agent optically active compound
  • various known chiral agents can be used as long as the chiral agent changes the HTP upon irradiation with light, and the chiral agent having a molar extinction coefficient at a wavelength of 313 nm of 30,000 or more. Agents are preferably used.
  • the chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase.
  • the chiral compound may be selected according to the purpose because the sense of the induced helix or the helix pitch varies depending on the compound.
  • the chiral agent a known compound can be used, but it preferably has a cinnamoyl group.
  • the chiral agent include a liquid crystal device handbook (Chapter 3, 4-3, Chiral agents for TN and STN, page 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989), and JP-A-2003-287623.
  • Compounds described in JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, JP-A-2010-181852, JP-A-2014-034581 and the like are exemplified. You.
  • the chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent.
  • Examples of the axially or planarly asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
  • the chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound, a repeating unit derived from the polymerizable liquid crystal compound, and a derivative derived from the chiral agent.
  • the polymerizable group of the polymerizable chiral agent is preferably a group of the same type as the polymerizable group of the polymerizable liquid crystal compound. Accordingly, the polymerizable group of the chiral agent is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and further preferably an ethylenically unsaturated polymerizable group. Further, the chiral agent may be a liquid crystal compound.
  • an isosorbide derivative As the chiral agent, an isosorbide derivative, an isomannide derivative, a binaphthyl derivative and the like can be preferably used.
  • an isosorbide derivative a commercially available product such as LC-756 manufactured by BASF may be used.
  • the content of the chiral agent in the liquid crystal composition is preferably from 0.01 to 200 mol%, more preferably from 1 to 30 mol%, based on the amount of the liquid crystal compound.
  • the liquid crystal composition preferably contains a polymerization initiator.
  • the polymerization initiator used is preferably a photopolymerization initiator capable of initiating the polymerization reaction by ultraviolet irradiation.
  • the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), and ⁇ -hydrocarbon-substituted aromatic compounds.
  • Group acyloin compounds described in US Pat. No.
  • JP-A-10-95788 JP-A-10-29997, JP-A-2001-233842, JP-A-2000-80068, JP-A-2006-342166, JP-A-2013-114249, JP-A-2014-137466, Japanese Patent No. 4223071, Japanese Patent Application Laid-Open No. 2010-262028, Japanese Patent Application Laid-Open No. 2014-500852), an oxime compound (Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent No. 4454067), and an oxadiazole compound ( U.S. Pat. No. 4,221,970).
  • the polymerization initiator for example, the description in paragraphs 0500 to 0547 of JP-A-2012-208494 can be referred to.
  • Examples of the polymerization initiator that can be used include an acylphosphine oxide compound and an oxime compound.
  • an acylphosphine oxide compound for example, a commercially available product IRGACURE810 (manufactured by BASF, compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) can be used.
  • Examples of the oxime compound include IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ADEKA ARKULS NCI-831, and ADEKA ARKULS NCI
  • IRGACURE OXE01 manufactured by BASF
  • IRGACURE OXE02 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • ADEKA ARKULS NCI-831 ADEKA ARKULS NCI
  • Commercially available products such as -930 (manufactured by ADEKA) and ADEKA ARKULS NCI-831 (manufactured by ADEKA) can be used.
  • One type of polymerization initiator may be used alone, or two or more types may be used in combination.
  • the HTP of the chiral agent is changed.
  • a photopolymerization initiator whose polymerization hardly proceeds by light irradiation for causing the polymerization.
  • the content of the photopolymerization initiator in the liquid crystal composition is preferably 0.05 to 3% by mass, more preferably 0.3 to 1.5% by mass, based on the content of the liquid crystal compound.
  • the content of the photopolymerization initiator in the liquid crystal composition is reduced by the content of the liquid crystal compound.
  • the content is preferably 0.01 to 0.3% by mass, more preferably 0.01 to 0.2% by mass.
  • the liquid crystal composition may optionally contain a crosslinking agent for improving the film strength and durability after curing.
  • a crosslinking agent for improving the film strength and durability after curing.
  • the cross-linking agent one that is cured by ultraviolet light, heat, moisture, or the like can be suitably used.
  • the crosslinking agent is not limited and can be appropriately selected according to the purpose.
  • polyfunctional acrylate compounds such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; epoxy compounds such as glycidyl (meth) acrylate and ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol Aziridine compounds such as tris [3- (1-aziridinyl) propionate] and 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate and biuret type isocyanate; polyoxazolines having an oxazoline group in a side chain Compounds; and alkoxysilanes such as vinyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane Such compounds are exemplified.
  • a known catalyst can be used depending on the reactivity of the crosslinking agent, so that productivity can be improved in addition to improvement in film strength and durability.
  • One type of catalyst may be used alone, or two or more types may be used in combination.
  • the content of the crosslinking agent in the liquid crystal composition is preferably from 3 to 20% by mass, more preferably from 5 to 15% by mass, based on the solid content of the liquid crystal composition.
  • an alignment controlling agent that contributes to a cholesteric liquid crystal structure of planar alignment stably or quickly may be added.
  • the alignment controlling agent include fluorine (meth) acrylate polymers described in paragraphs [0018] to [0043] of JP-A-2007-272185 and paragraph [0031] of JP-A-2012-203237. ] To [0034], etc., and the compounds represented by formulas (I) to (IV).
  • One kind of the orientation controlling agent may be used alone, or two or more kinds may be used in combination.
  • the addition amount of the alignment controlling agent in the liquid crystal composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and more preferably 0.02% by mass to 1% by mass based on the total mass of the liquid crystal compound. % Is more preferred.
  • the liquid crystal composition may include a surfactant.
  • the surfactant is preferably a compound that can function as an alignment control agent that contributes to a stable or prompt cholesteric structure of planar alignment.
  • Examples of the surfactant include a silicone-based surfactant and a fluorine-based surfactant, and a fluorine-based surfactant is preferable.
  • the surfactant include compounds described in paragraphs [0082] to [0090] of JP-A-2014-119605 and paragraphs [0031] to [0034] of JP-A-2012-203237. Compounds exemplified in paragraphs [0092] and [0093] of JP-A-2005-99248, paragraphs [0076] to [0078] and paragraphs [0082] to [0082] of JP-A-2002-129162. [0085] and fluorine (meth) acrylate-based polymers described in paragraphs [0018] to [0043] of JP-A-2007-272185, and the like.
  • one type may be used alone, or two or more types may be used in combination.
  • fluorine-based surfactant compounds represented by the following general formula (I) described in paragraphs [0082] to [0090] of JP-A-2014-119605 are particularly preferable.
  • L 11 , L 12 , L 13 , L 14 , L 15 , and L 16 each independently represent a single bond, —O—, —S—, —CO—, —COO—, — OCO-, -COS-, -SCO-, -NRCO-, -CONR- (R in the general formula (I) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
  • R in the general formula (I) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
  • -NRCO- and -CONR- have the effect of reducing the solubility, and the haze tends to increase during dot production.
  • —O—, —S—, —CO—, —COO—, —OCO—, —COS—, and —SCO— and more preferably —O—, —CO—, —COO—, and —OCO—.
  • the alkyl group which R can take may be linear or branched.
  • the number of carbon atoms is more preferably 1 to 3, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.
  • Sp 11 , Sp 12 , Sp 13 and Sp 14 each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably a single bond or an alkylene group having 1 to 7 carbon atoms, further preferably Is a single bond or an alkylene group having 1 to 4 carbon atoms.
  • the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
  • the alkylene group may or may not be branched, but is preferably an unbranched linear alkylene group. From the viewpoint of synthesis, it is preferable that Sp 11 and Sp 14 are the same, and that Sp 12 and Sp 13 are the same.
  • a 11 and A 12 are a monovalent to tetravalent aromatic hydrocarbon group.
  • the number of carbon atoms of the aromatic hydrocarbon group is preferably from 6 to 22, more preferably from 6 to 14, even more preferably from 6 to 10, and particularly preferably 6.
  • the aromatic hydrocarbon groups represented by A 11 and A 12 may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group and an ester group. For the description and preferred ranges of these groups, reference can be made to the corresponding description of the T 11 below.
  • Examples of the substituent for the aromatic hydrocarbon group represented by A 11 or A 12 include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, and a cyano group.
  • a molecule having a large number of perfluoroalkyl moieties in the molecule can align the liquid crystal with a small amount of addition, which leads to a reduction in haze. Therefore, A 11 and A 12 have many perfluoroalkyl groups in the molecule. It is preferably tetravalent. From the viewpoint of synthesis, A 11 and A 12 are preferably the same.
  • T 11 represents a divalent group or a divalent aromatic heterocyclic group described below (X in T 11 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group Or an ester group, and Ya, Yb, Yc, and Yd each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
  • the number of carbon atoms of the alkyl group which X contained in T 11 can have is 1 to 8, preferably 1 to 5, and more preferably 1 to 3.
  • the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.
  • Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among them, a methyl group is preferred.
  • the alkyl moiety of the alkoxy group can take X contained in the T 11, reference may be made to the described preferred range of the alkyl group X can take contained in the T 11.
  • the halogen atom X can be taken to be included in the T 11, a fluorine atom, a chlorine atom, a bromine atom, and it is an iodine atom, a chlorine atom or a bromine atom, it is preferred.
  • the ester group X contained in the T 11 may take, may be mentioned groups represented by R a COO-.
  • the R a can be exemplified an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms which Ya, Yb, Yc and Yd can have may be linear or branched.
  • a methyl group, an ethyl group, an n-propyl group, and an isopropyl group can be exemplified.
  • the divalent aromatic heterocyclic group preferably has a 5-, 6- or 7-membered heterocyclic ring.
  • a 5- or 6-membered ring is more preferred, and a 6-membered ring is most preferred.
  • the hetero atom constituting the hetero ring a nitrogen atom, an oxygen atom or a sulfur atom is preferable.
  • the heterocycle is preferably an aromatic heterocycle.
  • the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Unsaturated heterocycles having the most double bonds are more preferred.
  • heterocycle examples include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, and a pyrazoline.
  • the divalent heterocyclic group may have a substituent.
  • substituents for the description of the examples of such substituents and the preferred range, reference can be made to the description and description of the substituents that the monovalent to tetravalent aromatic hydrocarbons of A 11 and A 12 can take.
  • Hb 11 represents a perfluoroalkyl group having 2 to 30 carbon atoms, more preferably a perfluoroalkyl group having 3 to 20 carbon atoms, and further preferably a perfluoroalkyl group having 3 to 10 carbon atoms.
  • the perfluoroalkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • m11 and n11 are each independently 0 to 3, and m11 + n11 ⁇ 1. At this time, a plurality of structures in parentheses may be the same or different, but are preferably the same.
  • General formula (I) m11, and n11 are determined by the A 11, and the valence of A 12, the preferred range is also the A 11, and determined by the valence of the preferred range of A 12.
  • O and p contained in T 11 are each independently an integer of 0 or greater, a plurality of X when o and p is 2 or more may be the same or different from each other.
  • O contained in the T 11 is preferably 1 or 2.
  • P contained in T 11 is preferably an integer of 1 to 4, more preferably 1 or 2.
  • the compound represented by the general formula (I) may have a symmetrical molecular structure or may have no symmetrical molecular structure.
  • the symmetry means at least one of point symmetry, line symmetry, and rotational symmetry, and the asymmetric does not correspond to any of point symmetry, line symmetry, and rotational symmetry. Means things.
  • the compound represented by the general formula (I) includes a perfluoroalkyl group (Hb 11 ), a linking group-(-Sp 11 -L 11 -Sp 12 -L 12 ) m11-A 11 -L 13 -and -L 14 -A 12 - (L 15 -Sp 13 -L 16 -Sp 14 -) n11-, and is preferably a compound which is a combination of T 11 is a divalent group having the excluded volume effect.
  • the two perfluoroalkyl groups (Hb 11 ) present in the molecule are preferably the same as each other, and the linking group — (— Sp 11 —L 11 —Sp 12 —L 12 ) m11-A 11 present in the molecule is preferred.
  • -L 13 - and -L 14 -A 12 - is preferably n11- also identical to each other - (L 15 -Sp 13 -L 16 -Sp 14).
  • the terminal Hb 11 -Sp 11 -L 11 -Sp 12 -and -Sp 13 -L 16 -Sp 14 -Hb 11 are preferably groups represented by any of the following general formulas.
  • a is preferably 2 to 30, more preferably 3 to 20, and still more preferably 3 to 10.
  • b is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 5.
  • a + b is 3 to 30.
  • r is preferably 1 to 10, more preferably 1 to 4.
  • terminal Hb 11 -Sp 11 -L 11 -Sp 12 -L 12 -and -L 15 -Sp 13 -L 16 -Sp 14 -Hb 11 of the general formula (I) are represented by any of the following general formulas The group represented by is preferred.
  • the amount of the surfactant added in the liquid crystal composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and more preferably 0.02 to 1% by mass based on the total mass of the liquid crystal compound. Is more preferred.
  • the liquid crystal composition may contain at least one selected from various additives such as a polymerizable monomer. Further, in the liquid crystal composition, if necessary, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring material, and metal oxide fine particles, etc., in a range that does not lower the optical performance. Can be added.
  • the solvent used for preparing the liquid crystal composition is not limited, and may be appropriately selected according to the liquid crystal compound to be added to the composition.
  • an organic solvent is preferably used.
  • the organic solvent is not particularly limited and may be appropriately selected depending on the liquid crystal compound to be added to the composition, and examples thereof include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, and hydrocarbons. , Esters, ethers and the like. Among them, ketones are particularly preferable in consideration of the burden on the environment.
  • One type of solvent may be used alone, or two or more types may be used in combination.
  • the first reflective layer 16 (cholesteric liquid crystal layer) is formed by applying a liquid crystal composition obtained by dissolving a liquid crystal compound, a chiral agent, a polymerization initiator, and, if necessary, a surfactant or the like in a solvent, to the underlayer 14. Then, the coating is dried to obtain a coating, and the coating is irradiated with actinic rays to cure the liquid crystal composition, thereby forming a coating. Thereby, the first reflective layer 16 having a cholesteric liquid crystal structure in which the cholesteric regularity is fixed can be formed.
  • the first reflective layer 16 having a wavy structure can be formed by applying the liquid crystal composition to form the first reflective layer 16 without subjecting the base layer 14 to an alignment treatment such as rubbing. As described above. Further, it is also described that the first reflective layer 16 having the PG structure can be formed by irradiating light that changes the HTP of the chiral agent prior to or simultaneously with the curing of the liquid crystal composition. It is as follows.
  • the second reflective layer 18 may be formed on the first reflective layer 16 after the first reflective layer 16 is formed. Since the second reflective layer 18 follows the orientation of the surface of the first reflective layer 16, the second reflective layer 18 also has a wavy structure as described above. When three or more reflective layers are formed, they may be formed on the reflective layer in the same manner.
  • the method for applying the liquid crystal composition is not particularly limited, and may be appropriately selected depending on the properties of the application composition, the materials for forming the underlayer 14 and the support 12, and the like.
  • a method of applying the liquid crystal composition for example, wire bar coating method, curtain coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, spin coating method, dip coating method, spray coating method, And a slide coating method.
  • the liquid crystal composition may be separately applied to the underlayer 14 (first reflection layer 16) by transferring the liquid crystal composition applied on the support. It is also possible to eject a liquid crystal composition.
  • An ink jet method is exemplified as a droplet ejection method.
  • the liquid crystal molecules are aligned.
  • the heating temperature is preferably 200 ° C. or lower, more preferably 130 ° C. or lower.
  • the liquid crystal composition is cured by polymerizing the aligned liquid crystal compound to form a reflective layer.
  • the polymerization of the polyfunctional liquid crystal compound may be either thermal polymerization or photopolymerization, but photopolymerization is preferred.
  • Light irradiation for curing the liquid crystal composition is preferably performed by ultraviolet irradiation.
  • Illuminance of ultraviolet rays is preferably 15 ⁇ 1500mW / cm 2, more preferably 100 ⁇ 600mW / cm 2.
  • the irradiation energy of ultraviolet rays is preferably from 20mJ / cm 2 ⁇ 50J / cm 2, more preferably 100 ⁇ 1500mJ / cm 2.
  • the wavelength of the ultraviolet light to be applied may be appropriately selected depending on the liquid crystal compound contained in the liquid crystal composition and the like.
  • a light source emitting light at 200 to 430 nm is preferably used, and a light source emitting light at 300 to 430 nm is more preferably used.
  • a short wavelength cut filter or the like is used in order to suppress the transmittance of light having a wavelength of 300 nm or less to 20% or less from the viewpoint of preventing decomposition and side reactions of the material used. You may.
  • a cholesteric liquid crystal layer having a PG structure When a cholesteric liquid crystal layer having a PG structure is formed, light that changes the HTP of the chiral agent is irradiated before the liquid crystal composition is cured.
  • light irradiation for changing the HTP of the chiral agent and light irradiation for curing the liquid crystal composition may be performed simultaneously.
  • the reflective layer it is preferable to perform irradiation with ultraviolet rays in order to promote the change of HTP of the chiral agent.
  • the oxygen concentration at the time of ultraviolet irradiation for promoting the change of the HTP of the chiral agent there is no limitation on the oxygen concentration at the time of ultraviolet irradiation for promoting the change of the HTP of the chiral agent. Therefore, this ultraviolet irradiation may be performed in an oxygen atmosphere or in a low oxygen atmosphere. Further, irradiation with ultraviolet rays for promoting the photopolymerization reaction of the liquid crystal compound is preferably performed under heating and / or under a low oxygen atmosphere.
  • the temperature at the time of ultraviolet irradiation is preferably maintained in a temperature range in which a cholesteric liquid crystal phase is exhibited so that the cholesteric liquid crystal layer is not disturbed.
  • the temperature at the time of ultraviolet irradiation is preferably 25 to 140 ° C, more preferably 30 to 100 ° C.
  • the low oxygen atmosphere at the time of ultraviolet irradiation may be formed by reducing the oxygen concentration in the atmosphere by a known method such as nitrogen replacement.
  • the oxygen concentration is preferably 5,000 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
  • the polymerization reaction rate after curing the liquid crystal composition is preferably higher, more preferably 50% or more, and still more preferably 60% or more.
  • the polymerization reaction rate can be found by measuring the consumption rate of the polymerizable functional group using an IR absorption spectrum.
  • the reflection sheet of the present invention can be used for various uses such as a decorative sheet, a light reflection member, a light diffusion plate, a half mirror, a transparent screen, an image sensor, a sensor, an optical device, and other optical elements.
  • the reflective sheet of the present invention is used for an optical device having a reflective sheet and an element utilizing light transmitted through the reflective sheet
  • the light transmitted through the reflective sheet is used by using the reflective sheet of the present invention.
  • the light reflected on the surface or the like of the element utilizing the light can be prevented from reaching the outside of the optical device, and the element utilizing the light transmitted through the reflection sheet can be hardly recognized.
  • the reflection sheet of the present invention may be used as a decorative sheet by bonding it to an optical filter such as an SC filter (manufactured by FUJIFILM Corporation) and an IR filter (manufactured by FUJIFILM Corporation). This makes it possible to decorate the device such as an image sensor and a sensor according to the light receiving wavelength.
  • an optical filter such as an SC filter (manufactured by FUJIFILM Corporation) and an IR filter (manufactured by FUJIFILM Corporation).
  • an image display device may be formed by using the reflection sheet of the present invention and an image display element.
  • Various known image display elements can be used as the image display element.
  • a liquid crystal display element and an organic electroluminescence display element are exemplified.
  • the reflection sheet of the present invention can also be used as an optical element.
  • it can be used for a general use as a half mirror and for a use described in paragraph [0017] of JP-A-2017-92021.
  • a PET film (Cosmoshine A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m was prepared.
  • This PET film has an easily adhesive layer on one surface.
  • the underlayer coating solution 1 having the following composition was applied to the surface of the PET film having no adhesive layer with a # 3.6 wire bar coater. Thereafter, the support was dried at 45 ° C. for 60 seconds, and irradiated with ultraviolet rays of 500 mJ / cm 2 at 25 ° C. by an ultraviolet irradiation device to prepare a support having a 1.4 ⁇ m-thick underlayer 1.
  • ⁇ Chiral agent> The following three kinds of chiral agents A to C were prepared. A first reflection layer and a second reflection layer described later were formed using any one of the chiral agents.
  • Chiral agent A and chiral agent B are chiral agents that form a right-handed spiral.
  • the chiral agent C is a chiral agent that forms a left-handed spiral.
  • the chiral agent B and the chiral agent C are chiral agents having a cinnamoyl group, and the chiral agent A is a chiral agent having no cinnamoyl group.
  • Table 1 shows the maximum molar extinction coefficients of the chiral agents A to C, the maximum wavelength representing the wavelength that becomes the maximum molar extinction coefficient, and the molar extinction coefficient at a wavelength of 313 nm.
  • ⁇ MAX indicates the maximum molar extinction coefficient
  • ⁇ @ 313 indicates the molar extinction coefficient at 313 nm.
  • Photopolymerization initiator A IRGACURE 907 (manufactured by Ciba-Geigy) Photopolymerization initiator B; Kayacure DETX (Nippon Kayaku)
  • the prepared coating liquid for the first reflective layer Ch-B was applied to the surface of the support having the underlayer 1 prepared above using a # 10.5 wire bar coater, and dried at 105 ° C. for 60 seconds. Thereafter, under a low oxygen atmosphere (100 ppm or less), light from a metal halide lamp having an irradiation amount of 60 mJ was irradiated through an optical filter SH0350 (manufactured by Asahi Spectroscopy) at 40 ° C., and further irradiated at 500 ° J. at 100 ° C. By irradiating light from a metal halide lamp, a first reflective layer which was a cholesteric liquid crystal layer was produced.
  • Methyl ethyl ketone 150.6 parts by mass Mixture of the above rod-shaped liquid crystal compound 100.0 parts by mass Photopolymerization initiator B 0.50 parts by mass Chiral agent C 11.00 parts by mass Surfactant F1 0.027 parts by mass Interface above Activator F2 0.067 parts by mass
  • the prepared reflection layer coating solution Ch-C was applied to the surface of the first reflection layer prepared above using a # 6 wire bar coater, and dried at 105 ° C. for 60 seconds. Thereafter, under a low oxygen atmosphere (100 ppm or less), light from a metal halide lamp having an irradiation amount of 60 mJ was applied through an optical filter SH0350 (manufactured by Asahi Spectroscopy) at 75 ° C., and further at an irradiation amount of 500 mJ at 100 ° C. By irradiating light from a metal halide lamp, a second reflective layer, which was a cholesteric liquid crystal layer, was formed, and a reflective sheet was produced.
  • SH0350 manufactured by Asahi Spectroscopy
  • the reflective layer coating solution Ch-C was applied to the support having the underlayer 1 prepared above using a # 10.5 wire bar coater, and dried at 105 ° C. for 60 seconds. Thereafter, under a low oxygen atmosphere (100 ppm or less), light from a metal halide lamp having an irradiation amount of 60 mJ at 75 ° C. is irradiated through an optical filter SH0350 (manufactured by Asahi Spectroscopy), and further, a metal halide having an irradiation amount of 500 mJ at 100 ° C. By irradiating light from a lamp, a first reflective layer, which was a cholesteric liquid crystal layer, was formed.
  • the coating liquid for reflective layer Ch-B was applied to the surface of the formed first reflective layer with a # 10.5 wire bar coater, and dried at 105 ° C. for 60 seconds. Thereafter, under a low oxygen atmosphere (100 ppm or less), light from a metal halide lamp having an irradiation amount of 60 mJ was irradiated through an optical filter SH0350 (manufactured by Asahi Spectroscopy) at 40 ° C., and further irradiated at 500 ° J. at 100 ° C. By irradiating light from a metal halide lamp, a second reflective layer, which was a cholesteric liquid crystal layer, was formed, and a reflective sheet was produced.
  • SH0350 manufactured by Asahi Spectroscopy
  • Example 2 ⁇ Examples 1 to 9, 11, and 12>
  • a first reflective layer and a second reflective layer which are cholesteric liquid crystal layers, were formed in the same manner except that the bar number of the wire bar coater was changed, to produce a reflective sheet.
  • a 50- ⁇ m-thick PC film (Technoloy, manufactured by Sumitomo Chemical Co., Ltd.) was used as the support instead of the PET film, and the number of the wire bar coater was # 13 in the preparation of the underlayer.
  • the underlayer 3 was produced in the same manner as the underlayer 1 except that the underlayer 3 was changed to.
  • the underlayer was not formed, and the first reflective layer was formed directly on the surface of the support (PET film).
  • the underlayer 2 was formed using the underlayer coating solution 2 described below instead of the underlayer 1. Details are shown in Table 2 below.
  • the integrated reflectance is the maximum integrated reflectance
  • the specular reflectance is the maximum specular reflectance.
  • the half width is the half width of the integrated reflection spectrum. Further, the distance between peaks is an average value of the distance between peaks of the wavy structure.
  • each of the reflection sheets of the present invention in which the thickness of the first reflection layer is smaller than that of the second reflection layer, has a wide selective reflection band, is excellent in diffuse reflectivity, and is free from defects in the wavy structure. It has excellent characteristics with no visible unevenness. Further, as shown in Examples 2 and 3, by making the second reflective layer 1 ⁇ m or more thicker than the first reflective layer, it is possible to more appropriately prevent the unevenness due to the wavy structure defect from being visually recognized. .
  • Example 5 and Example 10 by forming both the first reflection layer and the second reflection layer with the PG structure, the half width can be widened, that is, the selective reflection wavelength band can be further increased. Can be wide.
  • the first reflective layer as the lower reflective layer is thicker than the second reflective layer.
  • Comparative Example 2 in which the thicknesses of the reflective layers are equal, unevenness is visually recognized, and there is a problem in quality.
  • the support could be easily peeled off after applying an adhesive to the second reflective layer and attaching it to another sheet. . From the above results, the effect of the present invention is clear.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Optical Filters (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une feuille réfléchissante ayant une couche réfléchissante qui possède une large bande de longueurs d'onde réfléchies et une excellente propriété de réflexion diffuse, et dans laquelle des défauts sont imperceptibles. Le problème est résolu au moyen d'une feuille réfléchissante ayant une configuration dans laquelle une pluralité de couches réfléchissantes, dans lesquelles une phase de cristaux liquides cholestériques est immobilisée, sont empilées, dans laquelle : dans une section transversale de la couche réfléchissante lorsqu'elle est observée avec un microscope électronique à balayage, au moins une partie de sections claires et de sections sombres dérivées de la phase de cristaux liquides cholestériques ont une structure ondulée ; pour une ou plusieurs des couches réfléchissantes, le pas hélicoïdal varie dans la direction de l'épaisseur ; et une couche réfléchissante qui forme une surface avec une couche autre qu'une couche réfléchissante est plus mince que l'autre couche réfléchissante.
PCT/JP2019/032419 2018-09-28 2019-08-20 Feuille réfléchissante WO2020066367A1 (fr)

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WO2024090308A1 (fr) * 2022-10-26 2024-05-02 富士フイルム株式会社 Feuille décorative, dispositif d'affichage et décoration intérieure pour intérieur d'automobile

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WO2016017728A1 (fr) * 2014-07-31 2016-02-04 富士フイルム株式会社 Film, procédé de fabrication de film, film améliorant la luminance, élément de feuille optique et dispositif d'affichage à cristaux liquides
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WO2022024608A1 (fr) * 2020-07-30 2022-02-03 富士フイルム株式会社 Film décoratif, corps moulé décoratif, panneau décoratif et dispositif électronique
WO2024090308A1 (fr) * 2022-10-26 2024-05-02 富士フイルム株式会社 Feuille décorative, dispositif d'affichage et décoration intérieure pour intérieur d'automobile

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JP7175994B2 (ja) 2022-11-21
US20210223445A1 (en) 2021-07-22

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